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Examination of the normal coordinates shows that this is a reasonable approximation for the systems considered here.
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49
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3643096108
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- is equal to the difference in ΔH°.
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3643120045
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Note that the difference between these values is ∼10-15 kcal/mol, which is similar to the estimated strength of the hydrogen bonds in solution, refs 13 and 16.
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There are similar interesting observations involving proton-bound cluster ions where the structure is determined by interactions between multiple protonation sites of differing basicity. See: Böhringer, H.; Arnold, F. Nature 1981, 290, 321-322. Graul, S. T.; Squires, R. R. Int. J. Mass. Spectrom. Ion Proc. 1989, 94, 41-61.
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There are similar interesting observations involving proton-bound cluster ions where the structure is determined by interactions between multiple protonation sites of differing basicity. See: Böhringer, H.; Arnold, F. Nature 1981, 290, 321-322. Graul, S. T.; Squires, R. R. Int. J. Mass. Spectrom. Ion Proc. 1989, 94, 41-61.
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3643117971
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3643101272
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note
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The one-dimensional model may not produce quantitatively accurate vibrational frequencies, refs 50 and 51, and also neglects the other modes, such as bending, that are affected by isotopic substitution. However, these effects are expected to be small compared to the shift of the H/D stretching frequency, ref 66.
-
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-
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74
-
-
3643054316
-
-
note
-
Fluoroform is calculated to be less acidic than ethanol by 1.0 kcal/ mol at this level of theory compared to the experimental difference of -0.8 kcal/mol. This deficiency should not affect the conclusions from the calculated PES's.
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75
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77
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3643069993
-
-
note
-
Electrostatics do not provide a quantitative means to calculate the hydrogen bond strength since the charge distributions are certainly perturbed at the close range of interaction of the ion and neutral. They do, however, provide a useful model to interpret the energy difference between the two isomeric hydrogen bonded complexes.
-
-
-
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